U.S. patent application number 11/914147 was filed with the patent office on 2009-12-10 for multi-layer catalyst for producing phthalic anhydride.
This patent application is currently assigned to SUD-CHEMIE AG. Invention is credited to Marvin Estenfelder, Christian Guckel, Markus Niedermeier.
Application Number | 20090306409 11/914147 |
Document ID | / |
Family ID | 35788472 |
Filed Date | 2009-12-10 |
United States Patent
Application |
20090306409 |
Kind Code |
A1 |
Guckel; Christian ; et
al. |
December 10, 2009 |
MULTI-LAYER CATALYST FOR PRODUCING PHTHALIC ANHYDRIDE
Abstract
The present invention relates to a catalyst for preparing
phthalic anhydride by gas phase oxidation of o-xylene and/or
naphthalene, comprising at least three catalyst zones which have
different compositions and, from the gas inlet side toward the gas
outlet side, are referred to as first, second and third catalyst
zone, the catalyst zones having in each case an active composition
comprising TiO.sub.2 with a content of Na of less than 0.3% by
weight, and the active composition content decreasing from the
first catalyst zone disposed toward the gas inlet side to the third
catalyst zone disposed toward the gas outlet side, with the proviso
that (a) the first catalyst zone has an active composition content
between about 7 and 12% by weight, (b) the second catalyst zone has
an active composition content in the range between 6 and 11% by
weight, the active composition content of the second catalyst zone
being less than or equal to the active composition content of the
first catalyst zone, and (c) the third catalyst zone has an active
composition content in the range between 5 and 10% by weight, the
active composition content of the third catalyst zone being less
than or equal to the active composition content of the second
catalyst zone. Also described is a preferred process for preparing
such a catalyst and the preferred use of the titanium dioxide used
in accordance with the invention.
Inventors: |
Guckel; Christian; (Grafing,
DE) ; Niedermeier; Markus; (Bad Aibling, DE) ;
Estenfelder; Marvin; (Karlsruhe, DE) |
Correspondence
Address: |
SCOTT R. COX;LYNCH, COX, GILMAN & MAHAN, P.S.C.
500 WEST JEFFERSON STREET, SUITE 2100
LOUISVILLE
KY
40202
US
|
Assignee: |
SUD-CHEMIE AG
Munchen
DE
|
Family ID: |
35788472 |
Appl. No.: |
11/914147 |
Filed: |
November 28, 2005 |
PCT Filed: |
November 28, 2005 |
PCT NO: |
PCT/EP05/12703 |
371 Date: |
May 16, 2008 |
Current U.S.
Class: |
549/249 ;
502/159; 502/208; 502/344 |
Current CPC
Class: |
C07C 51/313 20130101;
B01J 27/198 20130101; B01J 23/002 20130101; C07C 51/265 20130101;
B01J 2523/00 20130101; C07C 63/16 20130101; B01J 2523/00 20130101;
B01J 2523/15 20130101; B01J 2523/47 20130101; B01J 2523/51
20130101; B01J 2523/55 20130101; B01J 2523/53 20130101; B01J
2523/47 20130101; C07C 63/16 20130101; B01J 2523/51 20130101; B01J
2523/53 20130101; B01J 2523/55 20130101; B01J 2523/00 20130101;
C07C 51/313 20130101; B01J 37/0219 20130101; B01J 35/0006 20130101;
C07C 51/265 20130101 |
Class at
Publication: |
549/249 ;
502/344; 502/208; 502/159 |
International
Class: |
C07D 307/89 20060101
C07D307/89; B01J 23/04 20060101 B01J023/04; B01J 27/14 20060101
B01J027/14; B01J 31/06 20060101 B01J031/06 |
Foreign Application Data
Date |
Code |
Application Number |
May 22, 2005 |
EP |
PCT/EP2005/005548 |
Claims
1. Catalysts for preparing phthalic anhydride by gas phase
oxidation of o-xylene and/or naphthalene, comprising a first
catalyst zone disposed toward a gas inlet side, a second catalyst
zone disposed closer to a gas outlet side and a third catalyst zone
disposed even closer to or at the gas outlet side, the catalyst
zones having different compositions, wherein the composition of
each catalyst zone comprises an active composition comprising
TiO.sub.2 with a content of Na of less than 0.3% by weight, wherein
the active composition content decreasing from the first catalyst
zone to the third catalyst zone, and wherein a) the first catalyst
zone has an active composition content between about 7 and 12% by
weight, b) the second catalyst zone has an active composition
content between 6 and 11% by weight, wherein the active composition
content of the second catalyst zone is less than or equal to the
active composition content of the first catalyst zone, and c) the
third catalyst zone has an active composition content in the range
between 5 and 10% by weight, wherein the active composition content
of the third catalyst zone is less than or equal to the active
composition content of the second catalyst zone.
2. The catalysts according to claim 1, characterized in that the
first catalyst zone has an active composition content between about
8 and 11% by weight.
3. The catalysts according to claim 1, characterized in that the
second catalyst zone has an active composition content between
about 7 and 10% by weight.
4. The catalysts according to claim 1, characterized in that the
third catalyst zone has an active composition content between about
6 and 9% by weight.
5. The catalysts according to claim 1, characterized in that the
active composition content decreases from catalyst zone to catalyst
zone in the direction of the gas flow.
6. The catalysts according to claim 1, characterized in that the
Cs-content (calculated as Cs) decreases from catalyst zone to
catalyst zone in the direction of the gas flow.
7. The catalysts according to claim 1, characterized in that only
the catalyst zone closest to the outlet side contains phosphorous
in an amount between 0.01 and 0.5% by weight, (calculated as
phosphorous).
8. The catalysts according to claim 1, characterized in that the
catalyst activity of the catalyst zone toward the gas inlet side is
lower than the catalyst activity of the catalyst zone toward the
gas outlet side.
9. The catalysts according to claim 1, characterized in that the
BET surface area of the first catalyst zone is lower than the BET
surface area of the third catalyst zone.
10. The catalysts according to claim 1, characterized in that the
BET surface area of the first and of the second catalyst zone is
the same, while the BET surface area of the third catalyst zone is
greater in comparison.
11. The catalysts according to claim 1, characterized in that the
BET surface area of the first and second catalyst zone is in each
case between about 15 and 25 m.sup.2/g, and the BET surface area of
the third catalyst zone is between about 25 and 45 m.sup.2/g.
12. The catalysts according to claim 1, characterized in that the
first catalyst zone disposed toward the gas inlet side has a length
fraction, based on the total length of the catalyst bed, of at
least 40%.
13. The catalysts according to claim 1, characterized in that the
proportion of the first catalyst zone in the total length of the
catalyst bed is between 40 and 70%.
14. The catalysts according to claim 1, characterized in that the
proportion of the second catalyst zone in the total length of the
catalyst bed is between about 10 and 40%.
15. The catalysts according to claim 1, characterized in that the
ratio of the length of the third catalyst zone to the length of the
second catalyst zone is between about 1 and 2.
16. The catalysts according to claim 1, characterized in that at
least about 40%, of the total pore volume of the TiO.sub.2 used is
formed by pores having a radius between 60 and 400 nm.
17. The catalysts according to claim 1, characterized in that up to
75%, of the total pore volume of the TiO.sub.2 used is formed by
pores having a radius between 60 and 400 nm.
18. The catalysts according to claim 1, characterized in that the
catalytically active composition is applied in a moving bed or
fluidized bed.
19. The catalysts according to claim 1, characterized in that less
than about 30%, of the total pore volume of the TiO.sub.2 is formed
by pores having a radius of more than 400 nm.
20. The catalysts according to claim 1, characterized in that about
17 to 27% of the total pore volume of the TiO.sub.2 is formed by
pores having a radius of more than 400 nm.
21. The catalysts according to claim 1, characterized in that about
50 to 75%, of the total pore volume of the TiO.sub.2 is formed by
pores having a radius of 60 to 400 nm.
22. The catalysts according to claim 1, characterized in that less
than 30%, of the total pore volume of the TiO.sub.2 is formed by
pores having a radius of 3.7 to 60 nm.
23. The catalysts according to claim 1, characterized in that about
10 to 30% of the total pore volume of the TiO.sub.2 is formed by
pores having a radius of 3.7 to 60 nm.
24. The catalysts according to claim 1, characterized in that the
D.sub.90 value of the TiO.sub.2 is between about 0.5 and 20
.mu.m.
25. The catalysts according to claim 1, characterized in that less
than 10%, of the total pore volume of the TiO.sub.2 is present by
virtue of micropores having a pore radius of less than 3.7 nm.
26. The catalysts according to characterized in that 8% by weight
or more of the catalytically active composition comprises vanadium,
calculated as vanadium pentoxide.
27. The catalysts according to claim 1, characterized in that at
least 0.05% by weight of the catalytically active composition is
formed from at least one alkali metal, calculated as alkali
metal(s).
28. The catalysts according to claim 1, characterized in that an
adhesive used with the catalytically active composition comprises
an organic polymer or copolymer.
29. The catalysts according to claim 1, calcined or conditioned in
an O.sub.2-containing gas, at >390.degree. C. for at least 24
hours.
30. The catalysts according to claim 1, wherein the active
composition further comprising niobium in an amount of 0.1 to 2% by
weight.
31. The catalysts according to claim 1, characterized in that only
one TiO.sub.2 source is used.
32. The catalysts according to claim 1, characterized in that no
phosphorus is present in the active composition.
33. A process for preparing phthalic anhydride by gas phase
oxidation comprising passing o-xylene and/or naphthalene over or
through the three-layer or multi-layer catalyst according to claim
1.
34. (canceled)
Description
[0001] The invention relates to a multi-layer catalyst, i.e. a
catalyst having three or more different layers (zones), for
preparing phthalic anhydride (PA) by gas phase oxidation of
o-xylene and/or naphthalene, the active composition content
decreasing from the first catalyst zone disposed toward the gas
inlet side to the catalyst zone disposed toward the gas outlet
side.
[0002] The industrial scale production of phthalic anhydride is
achieved by the catalytic gas phase oxidation of o-xylene and/or
naphthalene. For this purpose, a catalyst suitable for the reaction
is charged into a reactor, preferably what is known as a tube
bundle reactor in which a multitude of tubes are arranged in
parallel, and is flowed through from the top or bottom with a
mixture of the hydrocarbon(s) and an oxygenous gas, for example
air. Owing to the intense heat formation of such oxidation
reactions, it is necessary for a heat carrier medium to flow around
the reaction tubes to prevent what are known as hotspots and thus
to remove the amount of heat formed. This energy may be utilized
for the production of steam. The heat carrier medium used is
generally a salt melt and here preferably a eutectic mixture of
NaNO.sub.2 and KNO.sub.3.
[0003] To suppress the unwanted hotspots, it is likewise possible
to charge a structured catalyst into the reaction tube, as a result
of which, for example, two or three catalyst zones composed of
catalysts of different composition can arise. Such systems are as
such already known from EP 1 082 317 B1 or EP 1 084 115 B1.
[0004] The layer-by-layer arrangement of the catalysts also has the
purpose of keeping the content of undesired by-products, i.e.
compounds which are before the actual product of value in a
possible reaction mechanism of o-xylene to phthalic anhydride, in
the crude PA as low as possible. These undesired by-products
include mainly the compounds o-tolylaldehyde and phthalide. The
further oxidation of these compounds to phthalic anhydride
additionally increases the selectivity for the actual product of
value.
[0005] In addition to the above-addressed under-oxidation products,
over-oxidation products also occur in the reaction. These include
maleic anhydride, citraconic anhydride, benzoic acid and the carbon
oxides. A selective suppression of the formation of these undesired
by-products in favour of the product of value leads to a further
increase in the productivity and economic viability of the
catalyst.
[0006] EP 1 084 115 discloses a process for preparing phthalic
anhydride by catalytic gas phase oxidation of xylene and/or
naphthalene with a molecular oxygen-containing gas in a fixed bed
at elevated temperature and by means of at least three coated
catalysts arranged one on top of another in layers, to whose core
of support material a layer of catalytically active metal oxides
has been applied, characterized in that the catalyst activity
increases from layer to layer from the gas inlet side to the gas
outlet side, the activity of the catalysts of the individual layers
being adjusted in such a way that the catalyst having the lowest
activity has a lower active composition content and, if
appropriate, additionally more alkali metal, selected from the
group consisting of potassium, rubidium and caesium, as a dopant
than the catalyst of the next layer, and the even more active
catalyst which follows has the same amount of active composition
and even less alkali metal as a dopant or a larger amount of active
composition and, if appropriate, less alkali metal as a dopant than
the catalyst of the second layer, with the proviso that
a) the catalyst having the lowest activity, on non-porous support
material, has 5 to 9% by weight, based on the overall catalyst, of
active composition containing 3 to 8% by weight of V.sub.2O.sub.5,
0 to 3.5% by weight of Sb.sub.2O.sub.3, 0 to 0.3% by weight of P,
0.1 to 0.5% by weight of alkali (calculated as alkali metal) and,
as the remainder, TiO.sub.2 in anatase form having a BET surface
area of 18 to 22 m.sup.2/g, b) the next, more active catalyst, with
otherwise identical composition to catalyst (a), has an active
composition content higher by 1 to 5% by weight (absolute) and the
alkali content is lower by 0 to 0.25% by weight (absolute) and c)
the most active catalyst, with otherwise identical composition to
(a), has an active composition content higher by 1 to 5% by weight
(absolute) than for (a) and the alkali content is lower by 0.15 to
0.4% by weight (absolute) than for (a).
[0007] A disadvantage of the inventive catalysts specified there is
that, in spite of the use of such structured catalysts, very high
proportions of the undesired phthalide by-product are still present
in the crude PA. It is clear to those skilled in the art that a
distillative separation of the two products is possible only with
losses of the actual product of value. In addition, the PA yields
should be improved.
[0008] There is therefore a constant need for improved multi-layer
catalysts for the preparation of phthalic anhydride.
[0009] It is therefore an object of the present invention to
provide an improved catalyst for preparing phthalic anhydride by
gas phase oxidation of o-xylene and/or naphthalene, which avoids
the disadvantages of the prior art and in particular enables a high
selectivity and activity, even after a long operating time.
[0010] This object is achieved by the catalyst according to claim
1. Preferred embodiments are specified in the subclaims.
[0011] Thus, it has been found that, surprisingly, particularly
advantageous catalysts can be prepared when the catalyst is
composed of at least three different zones, the active composition
content decreasing from the first catalyst zone disposed toward the
gas inlet side to the catalyst zone disposed toward the gas outlet
side. It has been found to be essential that the first catalyst
zone has an active composition content between about 7 and 12% by
weight, in particular between about 8 and 11% by weight, the second
catalyst zone has an active composition content between about 6 and
11% by weight, in particular between about 7 and 10% by weight, and
the third or respectively last catalyst zone has an active
composition content between about 5 and 10% by weight, in
particular between about 6 and 9% by weight.
[0012] The terms first, second and third catalyst zone are used in
conjunction with the present invention as follows: the first
catalyst zone refers to the catalyst zone disposed toward the gas
inlet side. Toward the gas outlet side, the inventive catalyst
comprises another two further catalyst zones which are referred to
as the second and third catalyst zone. The third catalyst zone is
closer to the gas outlet side than the second catalyst zone.
[0013] In a particularly preferred inventive embodiment, the
inventive catalyst has three catalyst zones. In that case, the
third catalyst zone is at the gas outlet side. The presence of
additional catalyst zones downstream of the first catalyst zone in
the gas flow is, however, not ruled out. For example, in one
inventive embodiment, the third catalyst zone as defined herein may
be followed downstream by a fourth catalyst zone (having an active
composition content equal to or even lower than the third catalyst
zone).
[0014] According to the invention, the active composition content
may decrease between the first and the second catalyst zone and/or
between the second and the third catalyst zone.
[0015] In a particularly preferred inventive embodiment, the active
composition content decreases between the second and the third
catalyst zone. It goes without saying that the active composition
content never increases in the sequence of the catalyst zones from
the gas inlet side to the gas outlet side, but at best remains the
same. In a further preferred inventive embodiment the active
composition content decreases in the direction of the gas flow from
catalyst zone to catalyst zone, i.e. from the first to the last
catalyst zone.
[0016] It is assumed, without the invention being restricted to the
correctness of this assumption, that, as a result of the different
layer thicknesses, associated with the different active composition
contents, of the catalytically active composition in the individual
zones, more preferably the decreasing layer thicknesses of the
catalytically active composition from the first to the third zone,
influences firstly the reaction of o-xylene up to PA in the first
and, if appropriate, second zone, and the remaining under-oxidation
products are additionally oxidized in the third zone having the
even thinner layer of active composition, for example phthalide to
PA, but not PA to the over-oxidation products, for example
CO.sub.x. As a result, the maximum productivity in the oxidation of
o-xylene to PA is achieved over the overall structured packing at a
minimum proportion of the undesired by-products.
[0017] In a preferred inventive embodiment, the BET surface area
increases from the first catalyst zone disposed toward the gas
inlet side to the catalyst zone disposed toward the gas outlet side
(in particular the third or fourth catalyst zone). As a result, it
is surprisingly possible to achieve particularly good catalyst
performances. Preferred ranges for the BET surface area are 15 to
25 m.sup.2/g for the first catalyst zone, 15 to 25 m.sup.2/g for
the second catalyst zone and 25 to 45 m.sup.2/g for the third (or
respectively last) catalyst zone.
[0018] In general, it is preferred in accordance with the invention
that the BET surface area of the first catalyst zone is lower than
the BET surface area of the third (or respectively last) catalyst
zone. Particularly advantageous catalysts are also obtained when
the BET surface area of the first and of the second catalyst zone
is the same, while the BET surface area of the third catalyst zone
is greater in comparison. In particular (but not exclusively) when
more than three catalyst zones are present, it is also advantageous
in a preferred inventive embodiment that the BET surface area of
the last catalyst zone disposed toward the gas outlet side is
greater than the BET surface area of the catalyst zones disposed
closer to the gas inlet side. In a further embodiment, the BET
surface area of all catalyst zones apart from the last catalyst
zone disposed toward the gas outlet side may be the same.
[0019] The catalyst activity toward the gas inlet side is, in a
preferred inventive embodiment, lower than the catalyst activity
toward the gas outlet side. Thus, the catalyst activity increases
from the first to the last zone in this embodiment.
[0020] Preferably, the TiO.sub.2 used (Anatas modification) (in all
catalyst zones) has a content of alkali, especially of Na, of less
than 0.3% by weight, preferably less than 0.2% by weight,
preferably less than 0.15% by weight, further preferred less than
0.02% by weight, in particular less than 0.015% by weight. The
aforementioned threshold values preferably apply to Na and K. In a
further preferred inventive embodiment, the proportion of alkali
impurities (total alkali content) of the TiO.sub.2 used, calculated
as the sum of impurities of lithium, sodium, potassium, rubidium
and caesium, is less than 1000 ppm, preferably less than 500 ppm,
in particular less than 300 ppm. A method for determination of the
proportion of alkali impurities of the TiO.sub.2 used is given
below prior to the examples (DIN ISO 9964-3). The aforementioned
total alkali content of TiO.sub.2 enables the precise adjustment of
the alkali promotor content of the catalyst.
[0021] The proportion of alkali impurities, if necessary, may be
optionally lowered by washing with diluted nitric acid at elevated
temperature, as is known to those skilled in the art, to obtain the
preferred range of less than 1000 ppm. The TiO.sub.2 may e.g. be
slurried in 0.1 M HNO.sub.3 and washed under reflux and agitation
over night at 90.degree. C., subsequently filtered and washed
thrice with bidestillated water and dried at 150.degree. C. in air.
Then, the proportion of alkali impurities is determined again and,
if found too high, the afore procedure is repeated.
[0022] It has also been found that, surprisingly, the inventive
multi-layer catalysts with decreasing active composition content
can be used particularly advantageously for the preparation of
phthalic anhydride when the individual catalyst zones are present
in a certain length ratio relative to one another.
[0023] In general it has been found that especially good yields of
phthalic anhydride may be obtained if the length ratio of the first
and second zone is between 1.2 and 5 and that of the lengths of the
first and third zone is also between 1.2 and 5. Preferably, the
length ratio of the first and second zone is between 2 and 4, in
particular between 2.5 and 3.5. Preferably, the length ratio of the
first and third zone is between 2 and 4, in particular between 2.5
and 3.5.
[0024] Thus, in a particularly preferred inventive embodiment, the
first catalyst zone disposed toward the gas inlet side has a length
fraction, based on the total length of the catalyst bed, of at
least 40%, in particular at least 45%, more preferably at least
50%. It is especially preferred that the proportion of the first
catalyst zone in the total length of the catalyst bed is between 40
and 70%, in particular between 40 and 55%, more preferably between
40 and 52%.
[0025] The second zone takes up preferably about 10 to 40%, in
particular about 10 to 30%, of the total length of the catalyst
bed. It has also been found that, surprisingly, a ratio of the
length of the third catalyst zone to the length of the second
catalyst zone between about 1 and 2, in particular between 1.2 and
1.7, more preferably between 1.3 and 1.6, provides particularly
good results with regard to the economic viability, such as the
efficiency of raw material utilization and productivity of the
catalyst.
[0026] It has been found that, as the result of the above selection
of the length fractions of the individual catalyst zones, in
particular in combination with the decreasing active composition
contents as defined above, particularly favourable positioning of
the hotspot, in particular in the first zone, and good temperature
control for the avoidance of excessively high hotspot temperatures
are enabled even at prolonged operating time of the catalyst. As a
result, the yield, in particular based on the lifetime of the
catalyst, is improved. It is assumed, without the invention being
restricted to this assumption, that the above zone length ratio of
the individual catalyst zones relative to one another results in
virtually full conversion of the o-xylene used actually within the
second catalyst zone, and thus, in the third catalyst zone with the
above-described advantages, in what is known as "product
polishing", i.e. the cleaning of the reaction gas to remove
undesired by-products by oxidation to the actual product of value.
In addition, it is known to those skilled in the art that, after a
certain running time, such catalysts deactivate in the region of
the hotspot (generally in the first zone). This deactivation
results in a shifting of the reaction into the second, more active
zone, which leads to very high hotspot temperatures and the
associated problems in relation to selectivity and plant safety. As
a result of the zone ratios selected in the inventive catalyst, a
maximum residence time of the hotspot in the first zone with the
known advantages is ensured, and the inventive length of the second
and third zone simultaneously ensures a minimum proportion of
undesired by-products with simultaneously maximum yield of actual
product of value.
[0027] It has also been found that the zone length ratios defined
herein also exhibit advantages for other multi-layer catalysts,
i.e. which do not have the inventive decrease in the active
composition content. In addition to the catalysts for preparing
phthalic anhydride (PA) by gas phase oxidation of o-xylene and/or
naphthalene, this is also generally the case for other multi-layer
catalysts for the gas phase oxidation of hydrocarbons.
[0028] The temperature management in the gas phase oxidation of
o-xylene to phthalic anhydride is sufficiently well known to those
skilled in the art from the prior art, and reference can be made,
for example, to DE 100 40 827 A1.
[0029] In a further preferred embodiment, the active composition
(catalytically active composition) of the inventive catalyst
comprises titanium dioxide having a specific BET surface area and
preferably a specific pore radius distribution. It has been found
that, surprisingly, when titanium dioxide in which at least 25%, in
particular at least about 40%, more preferably at least about 50%,
most preferably at least about 60%, of the total pore volume is
formed by pores having a radius between 60 and 400 nm is used,
particularly advantageous catalysts can be obtained.
[0030] In a further preferred embodiment, TiO.sub.2 is used which
has a primary crystal size (primary particle size) of more than
about 210 angstrom, preferably more than about 250 angstrom, more
preferably at least 300 angstrom, in particular at least about 350
angstrom, further preferred at least about 390 angstrom. Thus, it
has been found that those TiO.sub.2 primary crystals having the
above (minimum) size enable the preparation of particularly
advantageous catalysts. The primary crystal size is preferably
below 900 angstrom, in particular below 600 angstrom, further
preferred below 500 angstrom. The above primary crystal size
apparently enables, without the invention being restricted to this
assumption, the formation of a not excessively compact, but rather
open-pored structure of the titanium dioxide in the catalyst. One
process for determining the primary crystal size is specified in
the method section which follows.
[0031] In a further preferred embodiment, TiO.sub.2 is used which
has a bulk density of less than 1.0 g/ml, in particular less than
0.8 g/ml, more preferably less than about 0.6 g/ml. Most preferred
are TiO.sub.2 materials having a bulk density of not more than
about 0.55 g/ml. One process for determining the bulk density is
specified in the method section which follows. It has thus been
found that the use of titanium dioxide having a bulk density as
defined above enables the preparation of particularly
high-performance catalysts. It is assumed, without a restriction of
the invention thereto, that the bulk density here is a measure of a
particularly favourable structure of the TiO.sub.2 surface made
available in the catalyst, the loose, not excessively compact
structure provides particularly favourable reaction spaces, and
access and escape routes for the reactants and reaction products
respectively.
[0032] It is assumed, without the invention being restricted to the
correctness of this theoretical assumption, that, as a result of
the use of the titanium dioxide having the properties described
herein in a catalyst, particularly advantageous reaction spaces can
be achieved for the desired reactions, in particular within the
pore structure. At the same time, when the inventive TiO.sub.2
matrix is used, advantageous access routes for the reactants to the
reactive sites on the surface of the TiO.sub.2 matrix, and also
escape routes for the reaction products, are provided.
[0033] In general, when the inventive catalyst is used to prepare
phthalic anhydride, a mixture of a molecular oxygen-containing gas,
for example air, and the starting material to be oxidized (in
particular o-xylene and/or naphthalene) is passed through a fixed
bed reactor, in particular a tube bundle reactor, which may consist
of a multitude of tubes arranged in parallel. In the reactor tubes
is disposed in each case a bed of at least one catalyst. The
preferences for a bed composed of a plurality of (different)
catalyst zones have already been addressed above.
[0034] When the inventive catalysts are used for preparing phthalic
anhydride by gas phase oxidation of o-xylene and/or naphthalene, it
has been found that, surprisingly, very good PA yields are achieved
with the inventive catalysts at very low contents of phthalide.
[0035] In a preferred inventive embodiment, the TiO.sub.2 used has
a BET surface area of at least 15 m.sup.2/g, preferably between 15
and 60 m.sup.2/g, in particular between about 15 and 45 m.sup.2/g
and more preferably between 15 and 30 m.sup.2/g. The BET surface of
the catalyst zone is largely determined by the BET surface of the
TiO.sub.2 used. In one inventive embodiment, the BET surface of the
catalyst zone is therefore equated with the BET surface of the
respective TiO.sub.2.
[0036] It is further preferred that up to 80%, preferably up to
75%, in particular up to 70% of the total pore volume of the
TiO.sub.2 is formed by pores having a radius between 60 and 400
nm.
[0037] The pore volumes and fractions reported herein, unless
stated otherwise, are determined by means of mercury porosimetry
(to DIN 66133). The total pore volume reported is based in the
present description in each case on the total pore volume, measured
by means of mercury porosimetry, between 7500 and 3.7 nm pore
radius size.
[0038] Pores having a radius of more than 400 nm constitute
preferably less than about 30%, in particular less than about 22%,
more preferably less than 20%, of the total pore volume of the
TiO.sub.2 used.
[0039] It is further preferred that about 50 to 75%, in particular
about 50 to 70%, more preferably from 50 to 65%, of the total pore
volume of the TiO.sub.2 is formed by pores having a radius of 60 to
400 nm, and preferably about 15 to 25% of the total pore volume by
pores having a radius of more than 400 nm.
[0040] With regard to the smaller pore radii, it is preferred that
less than 30%, in particular less than 20%, of the total pore
volume of the TiO.sub.2 is formed by pores having a radius of 3.7
to 60 nm. For this pore size, a range which is particularly
preferred here is about 10 to 30% of the total pore volume, in
particular 12 to 20%.
[0041] In a further preferred embodiment, the TiO.sub.2 used has
the following particle size distribution: the D.sub.10 value is
preferably 0.5 .mu.m or lower; the D.sub.50 value (i.e. the value
at which in each case half of the particles have a greater or
smaller particle diameter) is preferably 1.5 .mu.n or less; the
D.sub.90 value is preferably 4 .mu.m or less. The D.sub.90 value of
the TiO.sub.2 used is preferably between about 0.5 and 20 .mu.m, in
particular between about 1 and 10 .mu.m, more preferably between
about 2 and 5 .mu.m.
[0042] In electron micrographs, the TiO.sub.2 used in accordance
with the invention preferably has an open-pored, sponge-like
structure. The primary crystals are preferably combined to form
preferably open-pored agglomerates to an extent of more than 30%,
in particular more than 50%. It is assumed, without the invention
being restricted to this assumption, that this particular structure
of the TiO.sub.2 used, which is reflected in the pore radius
distribution, provides particularly favourable reaction conditions
for the gas phase oxidation.
[0043] In a further preferred inventive embodiment the first
catalyst zone does not contain phosphorus. It is further preferred
that also the second catalyst zone does not contain phosphorus. It
is particularly preferred that only the last catalyst layer
contains phosphorus, preferably between 0.01 and 0.5% by weight, in
particular between 0.1 and 0.4% by weight phosphorus (calculated as
phosphorus).
[0044] Depending on the intended use of the inventive catalyst, the
customary components familiar to those skilled in the art may be
present in the active composition of the catalyst in addition to
the TiO.sub.2 used in accordance with the invention. The shape of
the catalyst and its homogeneous or heterogeneous structure are
also in principle not restricted in the context of the present
invention and may include any embodiment which is familiar to those
skilled in the art and appears to be suitable for the particular
field of application.
[0045] For the preparation of phthalic anhydride, coated catalysts
in particular have been found to be useful. For these catalysts, a
support which is inert under the reaction conditions, for example
composed of quartz (SiO.sub.2), porcelain, magnesium oxide, tin
dioxide, silicon carbide, rutile, clay earth (Al.sub.2O.sub.3),
aluminium silicate, magnesium silicate (steatite), zirconium
silicate or cerium silicate, or composed of mixtures of the above
materials, is used. The support may, for example, have the shape of
rings, spheres, shells or hollow cylinders. To this is applied, in
comparatively thin layers (shells), the catalytically active
composition. It is also possible to apply two or more layers of
catalytically active composition having the same or different
compositions.
[0046] With regard to the further components of the catalytically
active composition of the inventive catalyst (in addition to
TiO.sub.2), it is possible in principle to refer to the
compositions and components which are described in the relevant
prior art and are familiar to those skilled in the art. They are
mainly catalyst systems which, in addition to titanium oxide(s),
comprise oxides of vanadium. Such catalysts are described, for
example, in EP 0 964 744 B1, whose disclosure on this subject is
hereby incorporated explicitly by reference into the
description.
[0047] In particular, the prior art describes a series of promoters
for increasing the productivity of the catalysts, which may
likewise be used in the inventive catalyst. These include the
alkali metals and alkaline earth metals, thallium, antimony,
phosphorus, iron, niobium, cobalt, molybdenum, silver, tungsten,
tin, lead and/or bismuth, and mixtures of two or more of the above
components. For example, DE 21 59 441 A describes a catalyst which,
in addition to titanium dioxide of the anatase modification,
consists of 1 to 30% by weight of vanadium pentoxide and zirconium
dioxide. It is possible via the individual promoters to influence
the activity and selectivity of the catalysts, in particular by
lowering or increasing the activity. The selectivity-increasing
promoters include, for example, the alkali metal oxides, whereas
oxidic phosphorus compounds, in particular phosphorus pentoxide,
increase the activity of the catalyst at the cost of the
selectivity.
[0048] For the preparation of the inventive catalysts, the prior
art describes numerous suitable processes, so that a detailed
description is in principle not required here. For the preparation
of coated catalysts, reference can be made, for example, to the
process described in DE-A-16 42 938 or DE-A 17 69 998, in which a
solution or suspension, comprising an aqueous and/or an organic
solvent, of the components of the catalytically active composition
and/or their precursor compounds (frequently referred to as
"slurry") are sprayed onto the support material in a heated coating
drum at elevated temperature until the desired content of
catalytically active composition, based on the total catalyst
weight, has been achieved. It is also possible, according to DE 21
06 796, to carry out the application (coating) of the catalytically
active composition to the inert support in fluidized bed
coaters.
[0049] Preference is given to preparing coated catalysts by the
application of a thin layer of 50 to 500 .mu.n of the active
components to an inert support (for example U.S. Pat. No.
2,035,606). In a preferred inventive embodiment, the thickness of
each coated layer (with the active composition) decreases according
to the decrease of the active composition content as described
herein from the first to the last catalyst zone. If the active
composition of the layers decreases, it is preferred that also the
thickness of the active composition decreases accordingly. Useful
supports have been found to be in particular spheres or hollow
cylinders. These shaped bodies give rise to a high packing density
at low pressure drop and reduce the risk of formation of packing
faults when the catalyst is charged into the reaction tubes.
[0050] The molten and sintered shaped bodies have to be
heat-resistant within the temperature range of the reaction as it
proceeds. As detailed above, possible substances are, for example,
silicon carbide, steatite, quartz, porcelain, SiO.sub.2,
Al.sub.2O.sub.3 or clay earth.
[0051] The advantage of the coating of support bodies in a
fluidized bed is the high uniformity of the layer thickness, which
plays a crucial role for the catalytic performance of the catalyst.
A particularly uniform coating is obtained by spraying a suspension
or solution of the active components onto the heated support at 80
to 200.degree. C. in a fluidized bed, for example according to DE
12 80 756, DE 198 28 583 or DE 197 09 589. In contrast to the
coating in coating drums, it is also possible, when hollow
cylinders are used as the support, to uniformly coat the inside of
the hollow cylinders in the fluidized bed processes mentioned.
Among the abovementioned fluidized bed processes, the process
according to DE 197 09 589 in particular is advantageous, since the
predominantly horizontal, circular motion of the supports achieves
not only a uniform coating but also low abrasion of apparatus
parts.
[0052] For the coating operation, the aqueous solution or
suspension of the active components and of an organic binder,
preferably a copolymer of vinyl acetate/vinyl laurate, vinyl
acetate/ethylene or styrene/acrylate, is sprayed via one or more
nozzles onto the heated, fluidized support. It is particularly
favourable to introduce the spray liquid at the point of the
highest product speed, as the result of which the sprayed substance
can be distributed uniformly in the bed. The spray operation is
continued until either the suspension has been consumed or the
required amount of active components has been applied on the
support.
[0053] In a particularly preferred inventive embodiment, the
catalytically active composition of the inventive catalyst is
applied in a moving bed or fluidized bed with the aid of suitable
binders, so that a coated catalyst is obtained. Suitable binders
include organic binders familiar to those skilled in the art,
preferably copolymers, advantageously in the form of an aqueous
dispersion, of vinyl acetate/vinyl laurate, vinyl acetate/acrylate,
styrene/acrylate, vinyl acetate/maleate and vinyl acetate/ethylene.
Particular preference is given to using an organic polymeric or
copolymeric adhesive, in particular a vinyl acetate copolymer
adhesive, as the binder. The binder used is added in customary
amounts to the catalytically active composition, for example at
about 10 to 20% by weight based on the solids content of the
catalytically active composition. For example, reference can be
made to EP 744 214. When the catalytically active composition is
applied at elevated temperatures of about 150.degree. C., it is
also possible, as is known from the prior art, to apply to the
support without organic binders. Coating temperatures which can be
used when the above-specified binders are used are, according to DE
21 06 796, for example, between about 50 and 450.degree. C. The
binders used burn off within a short time in the course of
baking-out of the catalyst when the charged reactor is put into
operation. The binders serve primarily to reinforce the adhesion of
the catalytically active composition on the support and to reduce
attrition in the course of transport and charging of the
catalyst.
[0054] Further possible processes for preparing coated catalysts
for the catalytic gas phase oxidation of aromatic hydrocarbons to
carboxylic acids and/or carboxylic anhydrides have been described,
for example, in WO 98/00778 and EP-A 714 700. According to these,
from a solution and/or a suspension of the catalytically active
metal oxides and/or their precursor compounds, optionally in the
presence of assistants for the catalyst preparation, a powder is
prepared initially and is subsequently, for the catalyst
preparation on the support, optionally after conditioning and also
optionally after heat treatment, applied in coating form to
generate the catalytically active metal oxides, and the support
coated in this way is subjected to a heat treatment to generate the
catalytically active metal oxides or to a treatment to remove
volatile constituents.
[0055] Suitable conditions for carrying out a process for preparing
phthalic anhydride from o-xylene and/or naphthalene are equally
familiar to those skilled in the art from the prior art. In
particular, reference is made to the comprehensive description in
K. Towae, W. Enke, R. Jackh, N. Bhargana "Phthalic Acid and
Derivatives" in Ullmann's Encyclopedia of Industrial Chemistry Vol.
A. 20, 1992, 181, and this is hereby incorporated by reference. For
example, the boundary conditions known from the above reference of
WO-A 98/37967 or of WO 99/61433 may be selected for the steady
operating state of the oxidation.
[0056] To this end, the catalysts are initially charged into the
reaction tubes of the reactor, which are thermostated externally to
the reaction temperature, for example by means of salt melts. The
reaction gas is passed over the thus prepared catalyst charge at
temperatures of generally 300 to 450.degree. C., preferably 320 to
420.degree. C., and more preferably of 340 to 400.degree. C., and
at an elevated pressure of generally 0.1 to 2.5 bar, preferably of
0.3 to 1.5 bar, with a space velocity of generally 750 to 5000
h.sup.-1.
[0057] The reaction gas fed to the catalyst is generally generated
by mixing a molecular oxygen-containing gas which, apart from
oxygen, may also comprise suitable reaction moderators and/or
diluents such as steam, carbon dioxide and/or nitrogen with the
aromatic hydrocarbon to be oxidized, and the molecular
oxygen-containing gas may generally contain 1 to 100 mol %,
preferably 2 to 50 mol % and more preferably 10 to 30 mol %, of
oxygen, 0 to 30 mol %, preferably 0 to 10 mol %, of steam, and 0 to
50 mol %, preferably 0 to 1 mol %, of carbon dioxide, remainder
nitrogen. To generate the reaction gas, the molecular
oxygen-containing gas is generally charged with 30 to 150 g per
m.sup.3 (STP) of gas of the aromatic hydrocarbon to be
oxidized.
[0058] In a particularly preferred inventive embodiment, the
inventive catalyst has an active composition content between about
7 and 12% by weight, preferably between 8 and 10% by weight, the
active composition (catalytically active composition) containing
between 5 and 15% by weight of V.sub.2O.sub.5, 0 and 4% by weight
of Sb.sub.2O.sub.3, 0.2 and 0.75% by weight of Cs, 0 and 3% by
weight of Nb.sub.2O.sub.5. Further to the aforementioned
components, the rest of the active composition contains at least
90% by weight, preferably at least 95% by weight, further preferred
at least 98% by weight, in particular at least 99% by weight,
further preferred at least 99.5% by weight, in particular 100% by
weight of TiO.sub.2. Such an inventive catalyst may, for example,
advantageously be used in a two-zone or multi-layer catalyst as the
first catalyst zone disposed toward the gas inlet side.
[0059] In a particularly preferred inventive embodiment, the BET
surface area of the catalyst is between 15 and about 25 m.sup.2/g.
It is further preferred that such a first catalyst zone has a
length fraction of about 40 to 60% in the total length of all
catalyst zones present (total length of the catalyst bed
present).
[0060] In a further preferred inventive embodiment, the inventive
catalyst has an active composition content of about 6 to 11% by
weight, in particular 7 to 9% by weight, the active composition
containing 5 to 15% by weight of V.sub.2O.sub.5, 0 to 4% by weight
of Sb.sub.2O.sub.3, 0.05 to 0.3% by weight of Cs, 0 to 2% by weight
of Nb.sub.2O.sub.5. Further to the aforementioned components, the
rest of the active composition contains at least 90% by weight,
preferably at least 95% by weight, further preferred at least 98%
by weight, in particular at least 99% by weight, further preferred
at least 99.5% by weight, in particular 100% by weight of
TiO.sub.2. Such an inventive catalyst may, for example, be used
advantageously as the second catalyst zone, i.e. downstream of the
first catalyst zone disposed toward the gas inlet side (see above).
It is preferred that the catalyst has a BET surface area between
about 15 and 25 m.sup.2/g. It is further preferred that this second
zone has a length fraction of about 10 to 30% of the total length
of all catalyst zones present.
[0061] In a further inventive embodiment, the inventive catalyst
has an active composition content between about 5 and 10% by
weight, in particular between 6 and 8% by weight, the active
composition (catalytically active composition) containing 5 to 15%
by weight of V.sub.2O.sub.5, 0 to 4% by weight of Sb.sub.2O.sub.3,
0 to 0.1% by weight of Cs, 0 to 1% by weight of Nb.sub.2O.sub.5.
Further to the aforementioned components, the rest of the active
composition contains at least 90% by weight, preferably at least
95% by weight, further preferred at least 98% by weight, in
particular at least 99% by weight, further preferred at least 99.5%
by weight, in particular 100% by weight of TiO.sub.2. Such an
inventive catalyst may be used, for example, advantageously as the
third (or respectively last) catalyst zone disposed downstream of
the above-described second catalyst zone. Preference is given to a
BET surface area of the catalyst which is somewhat higher than that
of the layers disposed closer to the gas inlet side, in particular
in the range between about 25 and about 45 m.sup.2/g. It is further
preferred that such a third catalyst zone has a length fraction of
about 10 to 50% of the total length of all catalyst zones
present.
[0062] It is further preferred in accordance with the invention
that, when the inventive catalyst is used in a multi-layer catalyst
bed, the content of alkali metals in the catalyst zones falls from
the gas inlet side toward the gas outlet side. In a particularly
preferred embodiment, the alkali content, especially the Cs-content
(calculated as Cs) in the second catalyst zone is less than in the
first catalyst zone, and in the third catalyst zone less than in
the second catalyst zone (and preferably, if applicable, in the
zones following the third zone). It is therefore particularly
preferred that the Cs-content (calculated as Cs) in the inventive
catalyst decreases from zone to zone in the direction of the gas
flow. In a preferred embodiment the third (and, if applicable, also
further catalyst zones) do not contain Cs. It is preferred
that:
Cs-content.sub.1st zone>Cs-content.sub.2nd zone> . . .
>CS-content.sub.last zone.
[0063] It is particularly preferred that the last catalyst zone
does not contain Cs.
[0064] In principle, it is possible in the inventive catalyst also
to use a different titanium dioxide with a different specification
than described above, i.e. a different BET surface area,
porosimetry and/or particle size distribution. However, it is
particularly preferred in accordance with the invention that at
least 50%, in particular at least 75%, more preferably all, of the
TiO.sub.2 used has a BET surface area and porosimetry as defined
herein, and preferably also the particle size distribution
described. It is also possible to use blends of different TiO.sub.2
materials.
[0065] It has also been found that, in a preferred embodiment, in
accordance with the invention, catalysts which do not have any
phosphorus in the catalytically active composition in combination
with the TiO.sub.2 used in accordance with the invention enable
particularly good activities at simultaneously very high
selectivity. It is further preferred that at least 0.05% by weight
of the catalytically active composition is formed by at least one
alkali metal, calculated as alkali metal(s). The particularly
preferred alkali metal is caesium.
[0066] In addition, according to the inventor's results, in one
embodiment, it is preferred that the inventive catalyst contains
niobium in an amount of 0.01 to 2% by weight, in particular 0.5 to
1% by weight, of the catalytically active composition.
[0067] The inventive catalysts are typically thermally treated or
calcined (conditioned) before use. It has been found to be
advantageous when the catalyst is calcined in an O.sub.2-containing
gas, in particular in air, at least 390.degree. C. for at least 24
hours, in particular at .gtoreq.400.degree. C. for between 24 and
72 hours. The temperature should preferably not exceed 500.degree.
C., in particular 470.degree. C. In principle, however, other
calcination conditions which appear to be suitable to those skilled
in the art are also not ruled out.
[0068] In a further aspect, the present invention relates to a
process for preparing a catalyst as described hereinbefore,
comprising the following steps: [0069] a. providing a catalytically
active composition as defined herein, [0070] b. providing an inert
support, in particular an inert shaped support body; [0071] c.
applying the catalytically active composition to the inert support,
in particular in a fluidized bed or a moving bed.
[0072] In a further aspect, the invention also relates to a process
for preparing phthalic anhydride by gas phase oxidation of o-xylene
and/or naphthalene, by using a three-layer or multi-layer catalyst
as defined in the present description.
[0073] In a further aspect, the present invention finally also
relates to the use of a catalyst as defined herein for preparing
phthalic anhydride by gas phase oxidation of o-xylene and/or
naphthalene.
Methods
[0074] To determine the parameters of the inventive catalysts, the
methods which follow are used:
1. BET Surface Area:
[0075] The determination is effected by the BET method according to
DIN 66131; a publication of the BET method can also be found in J.
Am. Chem. Soc. 60, 309 (1938).
2. Pore Radius Distribution:
[0076] The pore radius distribution and the pore volume of the
TiO.sub.2 used were determined by means of mercury porosimetry to
DIN 66133; maximum pressure: 2000 bar, Porosimeter 4000 (from
Porotec, Germany), according to the manufacturer's
instructions.
3. Primary Crystal Sizes:
[0077] The primary crystal sizes were determined by powder X-ray
diffractometry. The analysis was carried out with an instrument
from Bruker, Germany: BRUKER AXS-D4 Endeavor. The resulting X-ray
diffractograms were recorded with the "DiffracPlus D4 Measurement"
software package according to the manufacturer's instructions, and
the half-height width of the 100% refraction was evaluated with the
"DiffracPlus Evaluation" software by the Debye-Scherrer formula
according to the manufacturer's instructions in order to determine
the primary crystal size.
4. Particle Sizes:
[0078] The particle sizes were determined by the laser diffraction
method with a Fritsch Particle Sizer Analysette 22 Economy (from
Fritsch, Germany) according to the manufacturer's instructions,
also with regard to the sample pretreatment: the sample is
homogenized in deionized water without addition of assistants and
treated with ultrasound for 5 minutes.
5. Alkali Content of TiO.sub.2:
[0079] The alkali content of TiO.sub.2 is determined by DIN ISO
9964-3. Thus, an alkali determination is made by ICP-AES
(inductively Coupled Plasma Atomic Emission Spectroscopy) and, if
applicable, the total alkali content of TiO.sub.2 is added up.
6. Bulk Density:
[0080] The bulk density was determined with the aid of the
TiO.sub.2 used to prepare the catalyst (dried at 150.degree. C.
under reduced pressure, uncalcined). The resulting values from
three determinations were averaged.
[0081] The bulk density was determined by introducing 100 g of the
TiO.sub.2 material into a 1000 ml container and shaken for approx.
30 seconds (if required, several parallel batches).
[0082] A measuring cylinder (capacity precisely 100 ml) is weighed
empty to 10 mg. Above it, the powder funnel is secured over the
opening of the cylinder using a clamp stand and clamp. After the
stopwatch has been started, the measuring cylinder is charged with
the TiO.sub.2 material within 15 seconds. The spatula is used to
constantly supply more filling material, so that the measuring
cylinder is always slightly overfilled. After 2 minutes, the
spatula is used to level off the excess, care being taken that no
pressing forces compress the material in the cylinder. The filled
measuring cylinder is brushed off and weighed.
[0083] The bulk density is reported in g/ml.
[0084] The BET surface area, the pore radius distribution and the
pore volume, and also the particle size distribution were
determined for the titanium dioxide in each case on the uncalcined
material dried at 150.degree. C. under reduced pressure.
[0085] The data in the present description with regard to the BET
surface areas of the catalysts or catalyst zones also relate to the
BET surface areas of the TiO.sub.2 material used in each case
(dried at 150.degree. C. under reduced pressure, uncalcined, see
above).
[0086] In general, the BET surface area of the catalyst is
determined by virtue of the BET surface area of the TiO.sub.2 used,
although the addition of further catalytically active components
does change the BET surface area to a certain extent. This is
familiar to those skilled in the art.
[0087] The active composition content (content of the catalytically
active composition, without binder) relates in each case to the
content (in % by weight) of the catalytically active composition in
the total weight of the catalyst including support in the
particular catalyst zone, measured after conditioning at
400.degree. C. over 4 h.
[0088] The invention will now be illustrated in detail with
reference to the non-restrictive examples which follow:
EXAMPLES
Example 1
Preparation of Catalyst A
[0089] To prepare catalyst A having an active composition content
of 8% by weight and the composition of 7.5% by weight of vanadium
pentoxide, 3.2% by weight of antimony trioxide, 0.40% by weight of
caesium (calculated as caesium), 0.2% by weight of phosphorus
(calculated as phosphorus) and remainder titanium dioxide, 2600 g
of steatite bodies in the form of hollow cylinders of size
8.times.6.times.5 mm were coated at a temperature of 70.degree. C.
in a fluidized bed coater with a suspension of 17.9 g of vanadium
pentoxide, 7.6 g of antimony trioxide, 1.3 g of caesium sulphate,
1.9 g of ammonium dihydrogenphosphate, 211.1 g of titanium dioxide
having a BET surface area of 21 m.sup.2/g, 130.5 g of binder
composed of a 50% dispersion of water and vinyl acetate/ethylene
copolymer (Vinnapas.RTM. EP 65 W, from Wacker) and 2000 g of water.
The active composition was applied in the form of thin layers.
Example 2
Preparation of Catalyst B
[0090] To prepare catalyst B having an active composition content
of 8% by weight and the composition of 7.5% by weight of vanadium
pentoxide, 3.2% by weight of antimony trioxide, 0.20% by weight of
caesium (calculated as caesium), 0.2% by weight of phosphorus
(calculated as phosphorus) and remainder titanium dioxide, 2200 g
of steatite bodies in the form of hollow cylinders of size
8.times.6.times.5 mm were coated at a temperature of 70.degree. C.
in a fluidized bed coater with a suspension of 15.4 g of vanadium
pentoxide, 6.6 g of antimony trioxide, 0.5 g of caesium carbonate,
1.5 g of ammonium dihydrogenphosphate, 182.9 g of titanium dioxide
having a BET surface area of 21 m.sup.2/g, 110.7 g of binder
composed of a 50% dispersion of water and vinyl acetate/ethylene
copolymer (Vinnapas.RTM. EP 65 W, from Wacker) and 2000 g of water.
The active composition was applied in the form of thin layers.
Example 3
Preparation of Catalyst C
[0091] To prepare catalyst C having an active composition content
of 8% by weight and the composition of 7.5% by weight of vanadium
pentoxide, 3.2% by weight of antimony trioxide, 0.2% by weight of
phosphorus (calculated as phosphorus) and remainder titanium
dioxide, 2200 g of steatite bodies in the form of hollow cylinders
of size 8.times.6.times.5 mm were coated at a temperature of
70.degree. C. in a fluidized bed coater with a suspension of 13.35
g of vanadium pentoxide, 5.7 g of antimony trioxide, 1.34 g of
ammonium dihydrogenphosphate, 158.65 g of titanium dioxide having a
BET surface area of 21 m.sup.2/g, 109.4 g of binder composed of a
50% dispersion of water and vinyl acetate/ethylene copolymer
(Vinnapas.RTM. EP 65 W, from Wacker) and 2000 g of water. The
active composition was applied in the form of thin layers.
Example 4
Preparation of Catalyst D
[0092] To prepare catalyst D having an active composition content
of 9% by weight and the composition of 7.5% by weight of vanadium
pentoxide, 3.2% by weight of antimony trioxide, 0.40% by weight of
caesium (calculated as caesium), 0.2% by weight of phosphorus
(calculated as phosphorus) and remainder titanium dioxide, 2000 g
of steatite bodies in the form of hollow cylinders of size
8.times.6.times.5 mm were coated at a temperature of 70.degree. C.
in a fluidized bed coater with a suspension of 17.0 g of vanadium
pentoxide, 7.0 g of antimony trioxide, 1.1 g of caesium sulphate,
1.65 g of ammonium dihydrogenphosphate, 194.9 g of titanium dioxide
having a BET surface area of 21 m.sup.2/g, 102.1 g of binder
composed of a 50% dispersion of water and vinyl acetate/ethylene
copolymer (Vinnapas.RTM. EP 65 W, from Wacker) and 2000 g of water.
The active composition was applied in the form of thin layers.
Example 5
Preparation of Catalyst E
[0093] To prepare catalyst E having an active composition content
of 8% by weight and the composition of 7.5% by weight of vanadium
pentoxide, 3.2% by weight of antimony trioxide, 0.20% by weight of
caesium (calculated as caesium), 0.2% by weight of phosphorus
(calculated as phosphorus) and remainder titanium dioxide, 2000 g
of steatite bodies in the form of hollow cylinders of size
8.times.6.times.5 mm were coated at a temperature of 70.degree. C.
in a fluidized bed coater with a suspension of 15.1 g of vanadium
pentoxide, 6.3 g of antimony trioxide, 0.53 g of caesium sulphate,
1.47 g of ammonium dihydrogenphosphate, 173.7 g of titanium dioxide
having a BET surface area of 21 m.sup.2/g, 101 g of binder composed
of a 50% dispersion of water and vinyl acetate/ethylene copolymer
(Vinnapas.RTM. EP 65 W, from Wacker) and 2000 g of water. The
active composition was applied in the form of thin layers.
Example 6
Preparation of Catalyst F
[0094] To prepare catalyst F having an active composition content
of 8% by weight and the composition of 7.5% by weight of vanadium
pentoxide, 3.2% by weight of antimony trioxide, 0.2% by weight of
phosphorus (calculated as phosphorus) and remainder titanium
dioxide, 2000 g of steatite bodies in the form of hollow cylinders
of size 8.times.6.times.5 mm were coated at a temperature of
70.degree. C. in a fluidized bed coater with a suspension of 15.1 g
of vanadium pentoxide, 6.25 g of antimony trioxide, 1.47 g of
ammonium dihydrogenphosphate, 174.11 g of titanium dioxide having a
BET surface area of 27 m.sup.2/g, 101 g of binder composed of a 50%
dispersion of water and vinyl acetate/ethylene copolymer
(Vinnapas.RTM. EP 65 W, from Wacker) and 2000 g of water. The
active composition was applied in the form of thin layers.
Example 7
Preparation of Catalyst G
[0095] To prepare catalyst G having an active composition content
of 8% by weight and the composition of 7.5% by weight of vanadium
pentoxide, 3.2% by weight of antimony trioxide, 0.2% by weight of
phosphorus (calculated as phosphorus) and remainder titanium
dioxide, the procedure was exactly as above in Example 6 for
catalyst F, except that titanium dioxide having a BET surface area
of 21 m.sup.2/g was used.
Example 8
Catalytic Performance Data in the Oxidation of O-Xylene to Phthalic
Anhydride (Comparative Example 1)
[0096] A 450 cm-long reaction tube is charged successively with 100
cm of catalyst C, 60 cm of catalyst B and 130 cm of catalyst A. The
reaction tube is disposed in a liquid salt melt which can be heated
to temperatures up to 450.degree. C. In the catalyst bed is
disposed a 3 mm protective tube with an incorporated thermoelement,
which can be used to indicate the catalyst temperature over the
complete catalyst combination. To determine the catalytic
performance data, 0 to a maximum of 70 g/m.sup.3 (STP) of o-xylene
(purity 99.9%) are passed at 3.6 m.sup.3 (STP) of air/h over this
catalyst combination in the sequence ABC, and the reaction gas,
downstream of the reaction tube exit, is passed through a condenser
in which all organic constituents of the reaction gas apart from
the carbon monoxide and carbon dioxide are deposited. The deposited
crude product is melted off by means of superheated steam,
collected and subsequently weighed.
[0097] The crude yield is determined as follows.
Max. crude PA yield[by weight]=Weighed amount of crude
PA[g].times.100/feed of o-xylene[g].times.purity of
o-xylene[%/100]
[0098] In a further test (Example 8a) the lengths of the zones were
varied as follows: 90 cm catalyst C, 60 cm catalyst B, 140 cm
catalyst A. Otherwise, the procedure is as described under Example
8.
[0099] The results of the test run are listed in Table 1.
Example 9
Catalytic Performance Data in the Oxidation of O-Xylene to Phthalic
Anhydride (Inventive Example 1)
[0100] A 450 cm-long reaction tube is charged successively with 90
cm of catalyst F, 60 cm of catalyst E and 140 cm of catalyst D.
Otherwise, the procedure is as described under Example 8. The
results of the test run are listed in Table 1.
Example 10
Catalytic Performance Data in the Oxidation of O-Xylene to Phthalic
Anhydride (Comparative Example 2)
[0101] A 450 cm-long reaction tube is charged successively with 130
cm of catalyst C, 60 cm of catalyst B and 100 cm of catalyst A.
Otherwise, the procedure is as described under Example 8. The
results of the test run are listed in Table 1.
Example 11
Catalytic Performance Data in the Oxidation of O-Xylene to Phthalic
Anhydride (Inventive Example 2)
[0102] A 450 cm-long reaction tube is charged successively with 90
cm of catalyst G, 60 cm of catalyst E and 140 cm of catalyst D.
Otherwise, the procedure is as described under Example 8. The
results of the test run are listed in Table 1.
TABLE-US-00001 TABLE 1 PA quality Hotspot Maximum Crude PA
(phthalide value in temperature and Example loading yield the
reaction gas) location Example 8: 50 g/Nm.sup.3 112.4% by wt.
>2000 ppm 450.degree. C. Catalyst combination 150 cm (2nd zone)
A (130 cm) B (60 cm) C (100 cm) Example 8a: 54 g/Nm.sup.3 112.6% by
wt. >2200 ppm 447.degree. C. Catalyst combination 150 cm
(2.sup.nd zone) A (140 cm) B (60 cm) C (90 cm) Example 9: 57
g/Nm.sup.3 113.8% by wt. <500 ppm 440.degree. C. Catalyst
combination 50 cm (1st zone) D (140 cm) E (60 cm) F (90 cm) Example
10: 45 g/Nm.sup.3 106.7% by wt. >10000 ppm 450.degree. C.
Catalyst combination 150 cm (2nd zone) A (100 cm) B (60 cm) C (130
cm) Example 11: 58 g/Nm.sup.3 113.6% by wt. <800 ppm 440.degree.
C. Catalyst combination 50 cm (1st zone) D (140 cm) E (60 cm) G (90
cm)
[0103] As can be seen from Table 1, the inventive catalysts
according to Examples 9 and 11 show the highest PA yield and
highest PA quality. The hotspot is advantageously positioned in the
first catalyst zone. Inventive Example 9, in which the BET surface
area increases from the first to the third catalyst zone (here: is
higher in the third catalyst zone than in the first and second
catalyst zone), is even better with regard to the PA quality than
Inventive Example 11, in which the BET surface area does not rise
from the first toward the third catalyst zone.
[0104] In the following Examples, the only feature that was changed
was the active composition content in the specific zones.
Example 12 (Comparative Example)
[0105] Catalysts used: Zone 1: Catalyst H, 9% by weight active
composition content Zone 2: Catalyst I, 10% by weight active
composition content Zone 3: Catalyst J, 11% by weight active
composition content
[0106] To prepare catalyst H having an active composition content
of 9% by weight and the composition of 7.5% by weight of vanadium
pentoxide, 3.2% by weight of antimony trioxide, 0.40% by weight
caesium (calculated as caesium), 0.2% by weight of phosphorus
(calculated as phosphorus) and remainder titanium dioxide, 2600 g
of steatite bodies in the form of hollow cylinders of size
8.times.6.times.5 mm were coated at a temperature of 70.degree. C.
in a fluidized bed coater with a suspension of 20.3 g of vanadium
pentoxide, 8.7 g of antimony trioxide, 1.5 g of caesium sulfate,
2.0 g of ammonium dihydrogenphosphate, 240.1 g of titanium dioxide
having a BET surface area of 21 m.sup.2/g, 132.1 g of binder
composed of a 50% dispersion of water and vinyl acetate/ethylene
copolymer (Vinnapas.RTM. EP 65 W, from Wacker) and 2000 g of water.
The active composition was applied in the form of thin layers.
[0107] To prepare catalyst I having an active composition content
of 10% by weight and the composition of 7.5% by weight of vanadium
pentoxide, 3.2% by weight of antimony trioxide, 0.20% by weight
caesium (calculated as caesium), 0.2% by weight of phosphorus
(calculated as phosphorus) and remainder titanium dioxide, 2600 g
of steatite bodies in the form of hollow cylinders of size
8.times.6.times.5 mm were coated at a temperature of 70.degree. C.
in a fluidized bed coater with a suspension of 22.8 g of vanadium
pentoxide, 9.7 g of antimony trioxide, 0.8 g of caesium sulfate,
2.3 g of ammonium dihydrogenphosphate, 270.3 g of titanium dioxide
having a BET surface area of 21 m.sup.2/g, 133.6 g of binder
composed of a 50% dispersion of water and vinyl acetate/ethylene
copolymer (Vinnapas.RTM. EP 65 W, from Wacker) and 2300 g of water.
The active composition was applied in the form of thin layers.
[0108] To prepare catalyst J having an active composition content
of 11% by weight and the composition of 7.5% by weight of vanadium
pentoxide, 3.2% by weight of antimony trioxide, 0.2% by weight of
phosphorus (calculated as phosphorus) and remainder titanium
dioxide, 2600 g of steatite bodies in the form of hollow cylinders
of size 8.times.6.times.5 mm were coated at a temperature of
70.degree. C. in a fluidized bed coater with a suspension of 25.4 g
of vanadium pentoxide, 10.8 g of antimony trioxide, 2.5 g of
ammonium dihydrogenphosphate, 301.4 g of titanium dioxide having a
BET surface area of 27 m.sup.2/g, 135.2 g of binder composed of a
50% dispersion of water and vinyl acetate/ethylene copolymer
(Vinnapas.RTM. EP 65 W, from Wacker) and 2500 g of water. The
active composition was applied in the form of thin layers.
Example 13 (Inventive Example)
[0109] Catalysts used: Zone 1: Catalyst K, 9% by weight active
composition content Zone 2: Catalyst L, 8% by weight active
composition content Zone 3: Catalyst M, 7% by weight active
composition content
[0110] To prepare catalyst K having an active composition content
of 9% by weight and the composition of 7.5% by weight of vanadium
pentoxide, 3.2% by weight of antimony trioxide, 0.40% by weight
caesium (calculated as caesium), 0.2% by weight of phosphorus
(calculated as phosphorus) and remainder titanium dioxide, 2600 g
of steatite bodies in the form of hollow cylinders of size
8.times.6.times.5 mm were coated at a temperature of 70.degree. C.
in a fluidized bed coater with a suspension of 20.3 g of vanadium
pentoxide, 8.7 g of antimony trioxide, 1.5 g of caesium sulfate,
2.0 g of ammonium dihydrogenphosphate, 240.1 g of titanium dioxide
having a BET surface area of 21 m.sup.2/g, 132.1 g of binder
composed of a 50% dispersion of water and vinyl acetate/ethylene
copolymer (Vinnapas.RTM. EP 65 W, from Wacker) and 2000 g of water.
The active composition was applied in the form of thin layers.
[0111] To prepare catalyst L having an active composition content
of 8% by weight and the composition of 7.5% by weight of vanadium
pentoxide, 3.2% by weight of antimony trioxide, 0.20% by weight
caesium (calculated as caesium), 0.2% by weight of phosphorus
(calculated as phosphorus) and remainder titanium dioxide, 2600 g
of steatite bodies in the form of hollow cylinders of size
8.times.6.times.5 mm were coated at a temperature of 70.degree. C.
in a fluidized bed coater with a suspension of 17.9 g of vanadium
pentoxide, 7.6 g of antimony trioxide, 0.6 g of caesium sulfate,
1.8 g of ammonium dihydrogenphosphate, 211.6 g of titanium dioxide
having a BET surface area of 21 m.sup.2/g, 132.1 g of binder
composed of a 50% dispersion of water and vinyl acetate/ethylene
copolymer (Vinnapas.RTM. EP 65 W, from Wacker) and 2000 g of water.
The active composition was applied in the form of thin layers.
[0112] To prepare catalyst M having an active composition content
of 7% by weight and the composition of 7.5% by weight of vanadium
pentoxide, 3.2% by weight of antimony trioxide, 0.2% by weight of
phosphorus (calculated as phosphorus) and remainder titanium
dioxide, 2600 g of steatite bodies in the form of hollow cylinders
of size 8.times.6.times.5 mm were coated at a temperature of
70.degree. C. in a fluidized bed coater with a suspension of 15.5 g
of vanadium pentoxide, 6.6 g of antimony trioxide, 1.6 g of
ammonium dihydrogenphosphate, 183.5 g of titanium dioxide having a
BET surface area of 27 m.sup.2/g, 129.1 g of binder composed of a
50% dispersion of water and vinyl acetate/ethylene copolymer
(Vinnapas.RTM. EP 65 W, from Wacker) and 1800 g of water. The
active composition was applied in the form of thin layers.
[0113] The 3-zone-catalysts of Examples 12 and 13 were used as
follows:
[0114] A 450 cm-long reaction tube is charged with 150 cm of
catalyst H (Example 12) and K (Example 13), respectively, 60 cm of
catalyst I (Example 12) and L (Example 13), respectively, and 80 cm
of catalyst J (Example 12) and M (Example 13), respectively.
Otherwise, the procedure is as described under Example 8. The
results of the test run are listed in Table 2.
TABLE-US-00002 TABLE 2 Maximum Crude PA Hotspot temperature Example
loading yield and location 12 (Comparative Example): 60 g/Nm.sup.3
109.4% by wt. 448.degree. C. Catalyst combination 55 cm (1st zone)
H (150 cm) I (60 cm) J (80 cm) 13 (Inventive Example): 60
g/Nm.sup.3 114.1% by wt. 450.degree. C. Catalyst combination 55 cm
(1st zone) K (150 cm), L (60 cm) M (80 cm)
[0115] As can be seen from Table 21 the inventive 3-zone-catalyst
according to Example 13 shows a much higher PA yield.
Example 14 (Comparative Example)
[0116] Catalysts used: Zone 1: Catalyst N, 8% by weight active
composition content Zone 2: Catalyst O, 9% by weight active
composition content Zone 3: Catalyst P, 10% by weight active
composition content
[0117] To prepare catalyst N having an active composition content
of 8% by weight and the composition of 7.5% by weight of vanadium
pentoxide, 3.2% by weight of antimony trioxide, 0.40% by weight
caesium (calculated as caesium) and remainder titanium dioxide,
2600 g of steatite bodies in the form of hollow cylinders of size
8.times.6.times.5 mm were coated at a temperature of 70.degree. C.
in a fluidized bed coater with a suspension of 17.9 g of vanadium
pentoxide, 7.6 g of antimony trioxide, 1.3 g of caesium sulfate,
211.6 g of titanium dioxide having a BET surface area of 21
m.sup.2/g, 130.5 g of binder composed of a 50% dispersion of water
and vinyl acetate/ethylene copolymer (Vinnapas.RTM. EP 65 W, from
Wacker) and 2000 g of water. The active composition was applied in
the form of thin layers.
[0118] To prepare catalyst O having an active composition content
of 9% by weight and the composition of 7.5% by weight of vanadium
pentoxide, 3.2% by weight of antimony trioxide, 0.20% by weight
caesium (calculated as caesium) and remainder titanium dioxide,
2600 g of steatite bodies in the form of hollow cylinders of size
8.times.6.times.5 mm were coated at a temperature of 70.degree. C.
in a fluidized bed coater with a suspension of 20.3 g of vanadium
pentoxide, 8.7 g of antimony trioxide, 0.7 g of caesium sulfate,
241.2 g of titanium dioxide having a BET surface area of 21
m.sup.2/g, 132.1 g of binder composed of a 50% dispersion of water
and vinyl acetate/ethylene copolymer (Vinnapas.RTM. EP 65 W, from
Wacker) and 2300 g of water. The active composition was applied in
the form of thin layers.
[0119] To prepare catalyst P having an active composition content
of 10% by weight and the composition of 7.5% by weight of vanadium
pentoxide, 0.2% by weight phosphorous (calculated as phosphorous)
and remainder titanium dioxide, 2600 g of steatite bodies in the
form of hollow cylinders of size 8.times.6.times.5 mm were coated
at a temperature of 70.degree. C. in a fluidized bed coater with a
suspension of 22.8 g of vanadium pentoxide, 2.3 g of ammonium
dihydrogenphosphate, 280.7 g of titanium dioxide having a BET
surface area of 27 m.sup.2/g, 133.6 g of binder composed of a 50%
dispersion of water and vinyl acetate/ethylene copolymer
(Vinnapas.RTM. EP 65 W, from Wacker) and 2500 g of water. The
active composition was applied in the form of thin layers.
Example 15 (Inventive Example)
[0120] Catalysts used: Zone 1: Catalyst Q, 8% by weight active
composition content Zone 2: Catalyst R, 8% by weight active
composition content Zone 3: Catalyst S, 7% by weight active
composition content
[0121] To prepare catalyst Q having an active composition content
of 8% by weight and the composition of 7.5% by weight of vanadium
pentoxide, 3.2% by weight of antimony trioxide, 0.40% by weight
caesium (calculated as caesium) and remainder titanium dioxide,
2600 g of steatite bodies in the form of hollow cylinders of size
8.times.6.times.5 mm were coated at a temperature of 70.degree. C.
in a fluidized bed coater with a suspension of 17.9 g of vanadium
pentoxide, 7.6 g of antimony trioxide, 1.3 g of caesium sulfate,
211.6 g of titanium dioxide having a BET surface area of 21
m.sup.2/g, 130.5 g of binder composed of a 50% dispersion of water
and vinyl acetate/ethylene copolymer (Vinnapas.RTM. EP 65 W, from
Wacker) and 2000 g of water. The active composition was applied in
the form of thin layers.
[0122] To prepare catalyst R having an active composition content
of 8% by weight and the composition of 7.5% by weight of vanadium
pentoxide, 3.2% by weight of antimony trioxide, 0.20% by weight
caesium (calculated as caesium) and remainder titanium dioxide,
2600 g of steatite bodies in the form of hollow cylinders of size
8.times.6.times.5 mm were coated at a temperature of 70.degree. C.
in a fluidized bed coater with a suspension of 17.9 g of vanadium
pentoxide, 7.6 g of antimony trioxide, 0.6 g of caesium sulfate,
212.1 g of titanium dioxide having a BET surface area of 21
m.sup.2/g, 130.5 g of binder composed of a 50% dispersion of water
and vinyl acetate/ethylene copolymer (Vinnapas.RTM. EP 65 W, from
Wacker) and 2000 g of water. The active composition was applied in
the form of thin layers.
[0123] To prepare catalyst S having an active composition content
of 7% by weight and the composition of 7.5% by weight of vanadium
pentoxide, 0.2% by weight phosphorous (calculated as phosphorous)
and remainder titanium dioxide, 2600 g of steatite bodies in the
form of hollow cylinders of size 8.times.6.times.5 mm were coated
at a temperature of 70.degree. C. in a fluidized bed coater with a
suspension of 15.5 g of vanadium pentoxide, 1.6 g of ammonium
dihydrogenphosphate, 190.1 g of titanium dioxide having a BET
surface area of 27 m.sup.2/g, 129.1 g of binder composed of a 50%
dispersion of water and vinyl acetate/ethylene copolymer
(Vinnapas.RTM. EP 65 W, from Wacker) and 1800 g of water. The
active composition was applied in the form of thin layers.
[0124] The 3-zone-catalysts of Examples 14 and 15 were used as
follows:
[0125] A 450 cm-long reaction tube is charged with 160 cm of
catalyst N (Example 14) and Q (Example 15), respectively, 60 cm of
catalyst O (Example 14) and R (Example 15), respectively, and 70 cm
of catalyst P (Example 14) and S (Example 15), respectively.
Otherwise, the procedure is as described under Example 8. The
results of the test run are listed in Table 3.
* * * * *